The electron donor–acceptor (EDA) complexes have been extensively studied, which formed an electronically excited state, obviating the need for an exogenous photocatalyst. Herein, we report a mild and efficient strategy for photoinduced radical domino perfluoroalkylation/cyclization using N,N,N′,N′-tetramethylethane-1,2-diamine (TMEDA) as an electron donor. This protocol could be well expanded to access various polycyclic quinazolinones containing perfluoroalkyl groups, exhibiting photocatalyst-free, good functional group tolerance, and environmentally friendly features.